Activation Energies of the Electrooxidation of Formic Acid on Pt(100)

The electrooxidation of small organic molecules on platinum surfaces usually involves different structure-dependent steps that include adsorption and desorption of various species and multiple reaction pathways. Because temperature plays a decisive role on each individual step, understanding its global influence on the reaction mechanism is often a difficult task, especially when the system is studied under far from equilibrium conditions in the presence of kinetic instabilities. Aiming at contributing to unravel this problem, herein, we report an experimental study of the role played by temperature on the electrooxidation of formic acid on a Pt(100) electrode. The system was investigated under both close and far from equilibrium conditions, and apparent activation energies were estimated using different strategies. Overall, comparable activation energies were estimated under oscillatory and quasi-stationary conditions, at high potentials. At low potentials, the poisoning process associated with the formic acid dehydration step presented a negligible dependence with temperature and, therefore, zero activation energy. On the basis of our experimental findings, we suggest that formic acid dehydration is the main, but maybe not the unique, step that differentiates the temperature dependence of the oscillatory electrooxidation of formic acid on Pt(100) with that on polycrystalline platinum.

Development of an Analytical Methodology for Quantification of Strong Acid in Diesel Oil

Many factors can affect the quality of diesel oil, in particular the degradation processes that are directly related to some organosulfur compounds. During the degradation process, these compounds are oxidized into their corresponding sulfonic acids, generating a strong acid content during the process. p-Toluene sulfonic acid analysis was performed using the linear sweep voltammetry technique with a platinum ultramicroelectrode in aqueous solution containing 3 mol L(-1) potassium chloride. An extraction step was introduced prior to the voltammetric detection in order to avoid the adsorption of organic molecules, which inhibit the electrochemical response. The extraction step promoted the transference of sulfonic acid from the diesel oil to an aqueous phase. The method was accurate and reproducible, with detection and quantification limits of 5 ppm and 15 ppm, respectively. Recovery of sulfonic acid was around 90%.

Effect of the catalyst composition in the Pt-x(Ru-Ir)(1-x)/C system on the electro-oxidation of methanol in acid media

The effect of variations in the composition for ternary catalysts of the type Pt-x(Ru-Ir)(1-x)/C on the methanol oxidation reaction in acid media for x values of 0.25, 0.50 and 0.75 is reported. The catalysts were prepared by the sol-gel method and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), atomic absorption spectroscopy (AAS) and energy dispersive X-ray (EDX) analyses. The nanometric character (2.8-3.2 nm) of the sol-gel deposits was demonstrated by XRD and TEM while EDX and AAS analyses showed that the metallic ratio in the compounds was very near to the expected one. Cyclic voltammograms for methanol oxidation revealed that the reaction onset occur at less positive potentials in all the ternary catalysts tested here when compared to a Pt-0.75-Ru-0.25/C (E-Tek) commercial composite. Steady-state polarization experiments (Tafel plots) showed that the Pt-0.25(Ru-Ir)(0.75)/C catalyst is the more active one for methanol oxidation as revealed by the shift of the reaction onset towards lower potentials. In addition, constant potential electrolyses suggest that the addition of Ru and Ir to Pt decreases the poisoning effect of the strongly adsorbed species generated during methanol oxidation. Consequently, the Pt-0.25 (Ru-Ir)(0.75)/C Composite catalyst is a very promising one for practical applications. (c) 2007 Elsevier B.V. All rights reserved.

An insight into the beginning stage of the aqueous ring opening metathesis polymerization of exo,exo-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid with Ru(III) compounds: the consumption of Ru(III) species in the presence of carboxylic acids monitored by ESR spectroscopy

The presence of paramagnetic species in the aqueous ring opening metathesis polymerizations of the exo,exo-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid monomer with RuCl(3) and K(2)[RuCl(5)H(2)O] compounds was studied using ESR techniques. It was observed that the intensities of the Ru(III) signals in the ESR spectra decrease on the time scale of the induction period so that the ROMP can take place. The intensity of the Ru(III) signal almost disappeared 50 min after reacting with K(2)[RuCl(5)H(2)O] and after 100 mm in the case of RuCl(3). Reactions of the cis-[Ru(NH(3))(4)(H(2)O)(2)](tfms)(3) and [Ru(NH(3))(5)H(2)O](tfms)(3) complexes with the monomer and different organic compounds representing the organic functions in the monomer (furan, norbornene, but-2-ene-1,4-diol and formic, acetic, oxalic and maleic acids) were also monitored by ESR and UV/vis spectra. It was deduced that the organic acids provide the disappearance of the Ru(III) signal. The proton NMR relaxation times of the residual water in D(2)O for reactions with oxalic acid suggested that the presence of paramagnetic ions in the solution decreases along with

Photocatalytic Decolorization of Commercial Acid Dyes using Solar Irradiation

This work investigates the solar heterogeneous photocatalytic degradation of three commercial acid dyes: Blue 9 (C.I. 42090), Red 51 (C.I. 45430), and Yellow 23 (C.I. 19140). TiO(2) P25 from Degussa was used as the photocatalyst. The dyes were completely degraded within 120 min of treatment in the following increasing order of removal rate: Blue 9 < Yellow 23 < Red 51. The photocatalytic color removal process was well described by a two-first-order in-series reaction, followed by another first-order reaction. Photolytic experiments showed that this process is quite inefficient and highly selective towards Red 51 only. The dyes` solution was completely decolorized and organic matter removals up to 99% were achieved with photocatalysis. The lack of selectivity and the possibility of using solar light to excite the photocatalyst are promising results regarding the feasibility of this technology.

Carbon supported electrocatalysts prepared by the sol-gel method and their utilization for the oxidation of methanol in acid media

One of the key objectives in fuel-cell technology is to improve the performance of the anode catalyst for the alcohol oxidation and reduce Pt loading. Here, we show the use of six different electrocatalysts synthesized by the sol -gel method on carbon powder to promote the oxidation of methanol in acid media. The catalysts Pt-PbO(x) and Pt-(RuO(2)-PbO(x)) with 10% of catalyst load exhibited significantly enhanced catalytic activity toward the methanol oxidation reaction as compared to Pt-(RuO(2))/C and Pt/C electrodes. Cyclic voltammetry studies showed that the electrocatalysts Pt-PbO(x)/C and Pt-(RuO(2)-PbO(x))/C started the oxidation process at extremely low potentials and that they represent a good novelty to oxidize methanol. Furthermore, quasi-stationary polarization experiments and cronoamperometry studies showed the good performance of the Pt-PbO(x), Pt-(RuO(2)-PbO(x))/C and Pt-(RuO(2)-IrO(2))/C catalysts during the oxidation process. Thus, the addition of metallic Pt and PbO(x) onto high-area carbon powder, by the sol -gel route, constitutes an interesting way to prepare anodes with high catalytic activity for further applications in direct methanol fuel cell systems.

Silver Nanoparticles Obtained in PAH/PAA-Based Multilayers by Photochemical Reaction

Carboxylic acid groups in PAH/PAA-based multilayers bind silver cations by ion exchange with the acid protons. The aggregation and spatial distribution of the nanoparticles proved to be dependent oil the process used to reduce the silver acetate aqueous solution. The reducing method with ambient light formed larger nanoparticles with diameters ranging from 4-50 nm in comparison with the reduction method using UV light, which gave particles with diameters of 2-4 nm The high toughness of samples reduced by ambient light is a result of two population distributions of particle sizes caused by different mechanisms when compared with the UV light process. According to these phenomena, a judicious choice of the spectral source call be used as a way to control the type and size of silver nanoparticles formed on PEMs. Depending on the energy of the light source, the Ag nanoparticles present cubic and/or hexagonal crystallographic structures, as confirmed by XRD. Beyond the kinetically controlled process of UV photoinduced cluster formation, the annealing produced by UV light allowed a second mechanism to modify the growth rates, spatial distribution, and phases.

Comparison of prophylactic and therapeutic use of short-chain fatty acid enemas in diversion colitis: a study in Wistar rats

OBJECTIVES: To study the effect of short-chain fatty-acids on atrophy and inflammation of excluded colonic segments before and after the development of diversion colitis. INTRODUCTION: Diversion colitis is a chronic inflammatory process affecting the dysfunctional colon, possibly evolving with mucous and blood discharge. The most favored hypotheses to explain its development is short-chain fatty-acid deficiency in the colon lumen. METHODS: Wistar rats were submitted to colostomy with distal colon exclusion. Two control groups (A1 and B1) received rectally administered physiological saline, whereas two experimental groups (A2 and B2) received rectally administered short-chain fatty-acids. The A groups were prophylactically treated (5th to 40th days postoperatively), whereas the B groups were therapeutically treated (after post-operative day 40). The mucosal thickness of the excluded colon was measured histologically. The inflammatory reaction of the mucosal lamina propria and the lymphoid tissue response were quantified through established scores. RESULTS: There was a significant thickness recovery of the colonic mucosa in group B2 animals (p = 0.0001), which also exhibited a significant reduction in the number of eosinophilic polymorphonuclear cells in the lamina propria (p = 0.0126) and in the intestinal lumen (p = 0.0256). Group A2 showed no mucosal thickness recovery and significant increases in the numbers of lymphocytes (p = 0.0006) and eosinophilic polymorphonuclear cells in the lamina propria of the mucosa (p = 0.0022). CONCLUSION: Therapeutic use of short-chain fatty-acids significantly reduced eosinophilic polymorphonuclear cell numbers in the intestinal wall and in the colonic lumen; it also reversed the atrophy of the colonic mucosa. Prophylactic use did not impede the development of mucosal atrophy

Post consumer pet depolymerization by acid hydrolysis

The reaction of post-consumer poly(ethylene terephthalate) with aqueous solutions of sulfuric acid 7.5M was investigated in terms of temperature, time and particle size. The reaction extent reached 80% in four days at 100 degrees C and 90% in 5 hours at 135 degrees C. TPA obtained was purified and considered in the same level of quality of the commercial one after tests of elemental analysis, particle size and color. It was concluded that the hydrolysis occurred preferentially at the chain ends and superficially, having as controller mechanism the acid diffusion into the polymer structure. The shrinking-core model can explain the reaction kinetics.

The role of sugar cane straw on soil reaction

Conduziram-se dois experimentos em laboratório avaliar o efeito da palha da cana- de-açúcar na acidez do solo. A palha da cana foi adicionada nas doses de 0, 20, 40, e 76 g kg-1 na superfície de um latossolo roxo distrófico acondicionado em colunas de PVC. O solo foi incubado a capacidade de campo durante 0, 7, 14, 45, e 90 dias. Após cada incubação, o solo das colunas foram subdividido e amostrado nas seguintes frações 0-5, 5-10, 10-15, 15-20, e 20-25 cm. Com o aumento da dose da palha da cana verificou-se aumento do pH CaCl2 do solo e decréscimo do alumínio trocável até a camada de 15 cm de solo da coluna de PVC. A contribuição de compostos orgânicos para a destoxificação do Al aumentou com o acréscimo das doses da palha da cana. O crescimento da raiz das plantas trigo usadas como planta indicadora aumentou com o acréscimo das doses da palha de cana. O máximo de crescimento da raiz foi até a camada de 15 cm de solo depois de oito dias para a maior dose de palha da cana-de-açúcar.

Niobium Pentachloride Catalyzed Multicomponent Povarov Reaction

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Thermal analysis as a screening technique for the characterization of babassu flour and its solid fractions after acid and enzymatic hydrolysis

The babassu (Orbignya phalerata) is a native tree found in northern Brazil. Extracts of the babassu coconut have been widely used in industry. Babassu flour has about 60% starch, thus, besides nourishment it can be used as an alternative biofuel source. However, the properties of this starch lack of study and understanding. The main purpose of this study was to investigate the thermal behavior of raw babassu flour and its solid hydrolyzed fraction. The analyses were carried out using SHIMADZU DSC and TG thermic analyzers. The results demonstrated a reduction in thermal stability of the solid hydrolyzed fraction compared to raw matter. The kinetic parameters were investigated using non-isothermal methods and the parameters obtained for its decomposition process were an E(a) of 166.86 kJ mol(-1) and a frequency factor (beta) of 6.283 x 1014 min(-1); this was determined to be a first order reaction (n = 1). (C) 2011 Elsevier B.V. All rights reserved.

Optimization of acid hydrolysis from the hemicellulosic fraction of Eucalyptus grandis residue using response surface methodology

Biotechnological conversion of biomass into fuels and chemicals requires hydrolysis of the polysaccharide fraction into monomeric sugars. Hydrolysis can be performed enzymatically and with dilute or concentrate mineral acids. The present study used dilute sulfuric acid as a catalyst for hydrolysis of Eucalyptus grandis residue. The purpose of this paper was to optimize the hydrolysis process in a 1.41 pilot-scale reactor and investigate the effects of the acid concentration, temperature and residue/acid solution ratio on the hemicellulose removal and consequently on the production of sugars (xylose, glucose and arabinose) as well as on the formation of by-products (furfural, 5-hydroxymethylfurfural and acetic acid). This study was based on a model composition corresponding to a 2 3 orthogonal factorial design and employed the response surface methodology (RSM) to optimize the hydrolysis conditions, aiming to attain maximum xylose extraction from hemicellulose of residue. The considered optimum conditions were: H2SO4 concentration of 0.65%, temperature of 157 degrees C and residue/acid solution ratio of 1/8.6 with a reaction time of 20 min. Under these conditions, 79.6% of the total xylose was removed and the hydrolysate contained 1.65 g/l glucose, 13.65 g/l xylose, 1.55 g/l arabinose, 3.10 g/l acetic acid, 1.23 g/l furfural and 0.20 g/l 5-hydroxymethylfurfural. (c) 2006 Published by Elsevier Ltd.

Evaluation of the kinetics of xylose formation from dilute sulfuric acid hydrolysis of forest residues of Eucalyptus grandis

Dilute acid hydrolysis studies were performed on forest residues of Eucalyptus grandis, in a cylindrical reactor of stainless steel. The kinetics of this hydrolysis reaction was investigated employing 0.65% sulfuric acid, a residue/acid solution ratio of 1/9 (w/w), temperatures of 130, 140, 150, and 160 degrees C, and reaction times in the range 20-100 min. The results showed that, under the optimized conditions of acid hydrolysis employed in this study, the variables temperature and reaction time had a strong influence on hemicellulose removal and a small influence on the degree of lignin and cellulose removal. The highest xylose extraction yield was 87.6% attained at 160 degrees C, after 70 min reaction time, simultaneously with the formation of decomposition products, namely 2.8% acetic acid, 0.6% furfural, and 0.06% 5-hydroxymethylfurfural. A similar xylose extraction yield (82.8%) was observed at 150 degrees C after 100 min, with the formation of 3.2% acetic acid, 1.0% furfural, and 0.07% 5-hydroxymethylfurfural. The kinetic parameters determined at 130, 140, 150, and 160 degrees C for degradation of xylan present in the hemicellulose of the eucalyptus forest residue during the formation of xylose were the first-order reaction rate constants (k) for each temperature, 1.22 x 10(-4), 2.12 x 10(-4), 5.43 x 10(-4), and 9.05 x 10(-4) s(-1), respectively, and an activation energy (E-a) of 101.3 kJ mol(-1).

Avaliação oxidativa do biodiesel de pinhão manso em diferentes processos de purificação

The objective of this study was to analyze the oxidative stability of biodiesel from jatropha obtained from different purification processes, three wet processes with different drying (in a vacuum oven, conventional oven and in anhydrous sodium sulfate) and dry (purification with magnesium silicate adsorbent). Raw materials of different qualities (jatropha crop ancient and recent crop) were used. The Jatropha oil was extracted by mechanical extraction and refined. The Jatropha biodiesel was obtained by the transesterification reaction in ethyl route using alkaline catalysis. The biodiesel samples were characterized by analysis of water content, carbon residue, Absorption Spectroscopy in the Infrared Region and Thermogravimetry. Thermogravimetric curves of purified PUsv* PUsq* and had higher initial decomposition temperatures, indicating that the most stable, followed by samples PU* and PUSC*. Besides the sample SP* is a smaller initial temperature, confirming the sample without purification to be less thermally stable. The percentage mass loss of the purified samples showed conversion of about 98.5%. The results of analyzes carbon residue and infrared suggested that contamination by impurities is the main factor for decreased oxidative stability of biodiesel. The oxidative stability was assessed from periodic monitoring, using the techniques of Rancimat, peroxide index, acid value and Pressurized Differential Scanning Calorimetry. Samples of biodiesel from jatropha which showed better oxidative stability were of the best quality raw material and wet scrubbing: PUsq* with dry chemical, using anhydrous sodium sulfate and PUsv* with vacuum drying, which had oxidative stability 6 hours in Rancimat time 0 days, within the limits established by the Technical Regulation No. 4/2012 of the ANP, without the addition of antioxidant, suggesting that these procedures the least influence on the oxidative stability of biodiesel